JP2003004199A - Hydrogen cylinder and hydrogen gas storage method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen cylinder and a hydrogen gas storage method capable of easily generating and storing hydrogen gas in a pressure-resistant container when necessary even without a hydrogen supply source. SOLUTION: A hydrogen cylinder 1 is provided with a pressure-resistant container 2 provided with a gas discharge hole 21 and a material charging port 22, a catalyst 3 disposed in the pressure-resistant container 2, and an N 2 previously charged into and built into the pressure-resistant container 2.
having a powder 4 made of ABH _4. When hydrogen gas is generated in the hydrogen cylinder 1, water 5 is supplied from the material inlet 22.
Is injected into the pressure-resistant container 2 so that NaB
The H ₄ powder 4 is brought into contact with the water 5 to cause a hydrolysis reaction in the presence of the catalyst 3. The hydrogen cylinder 1 is configured to generate and store hydrogen gas in the pressure vessel 2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrogen cylinder for producing and storing hydrogen gas by bringing NaBH ₄ into contact with water and carrying out a hydrolysis reaction, and a method for storing hydrogen gas.

[0002]

2. Description of the Related Art Most of hydrogen is stored in a gaseous state. In this case, in order to fill as much hydrogen gas as possible into the pressure vessel having a limited volume, the hydrogen gas is pressurized by using a compressor or the like, and the pressure is about 15 to 20 MPa.
It is stored as high pressure gas (gauge pressure) in a hydrogen cylinder consisting of a pressure container. Further, if hydrogen is stored in a gas state, a large pressure resistant container is required. Therefore, there is also a method of liquefying hydrogen and storing it in a special container having high heat insulation.
In this method, hydrogen can be liquefied at an extremely low temperature of −253 ° C., made into a volume of about 1/800 with respect to hydrogen gas under normal pressure, and stored in a hydrogen cylinder made of the above special container. .

[0003]

However, in any of the conventional hydrogen storage methods described above, hydrogen is externally filled in a container for storage, and the hydrogen is released to the outside when used. Therefore, when using a conventional hydrogen cylinder, it is necessary to prepare hydrogen to be filled and to fill it in advance. Therefore, it cannot be used as a hydrogen cylinder without a hydrogen supply source.

The present invention has been made in view of the above-mentioned conventional problems, and it is possible to easily generate and store hydrogen gas in a pressure-resistant container when necessary, without a hydrogen supply source. And a method for storing hydrogen gas.

[0005]

According to a first aspect of the present invention, there is provided a pressure resistant container having a gas discharge hole and a material charging port, and a catalyst disposed in the pressure resistant container, and NaBH ₄ and water are charged from the material charging port. The NaBH ₄ is brought into contact with water to cause a hydrolysis reaction in the presence of the catalyst to generate and store hydrogen gas in the pressure resistant container. It is in a hydrogen cylinder (claim 1).

Next, the function and effect of the present invention will be described.
The hydrogen cylinder according to the present invention can directly generate hydrogen gas in the pressure resistant container without filling the hydrogen gas from the outside of the pressure resistant container. That is, in the present invention, hydrogen gas is generated by introducing NaBH ₄ and water into a pressure vessel and bringing them into contact with each other to carry out a hydrolysis reaction. At this time, since the catalyst is placed in the pressure vessel, the hydrolysis reaction can be promoted to rapidly generate hydrogen gas.

As described above, in the present invention, it is possible to generate hydrogen gas in the pressure resistant container and to fill the pressure resistant container with hydrogen gas without supplying hydrogen gas from the outside. Therefore, at a normal time when hydrogen gas is not required, it is possible to form a state in which there is no hydrogen gas in the pressure resistant container, and it is possible to eliminate the risk of storing hydrogen gas. Further, since hydrogen gas does not have to be supplied from the outside, a hydrogen gas supply source is not required.

Further, as described above, NaBH ₄ is brought into contact with water to generate hydrogen gas. Therefore, hydrogen gas can be easily generated by contacting NaBH ₄ with water only when necessary. Therefore, the present invention provides, for example,
It can be used for applications that require hydrogen gas in an emergency or emergency, or for portable use.

A second aspect of the present invention is a pressure resistant container having a gas discharge hole.
Vessel, a catalyst arranged in the pressure vessel, and the inside of the pressure vessel
Built-in Na separated from each other so that they do not touch each other
BH _FourAnd water and the NaBH_FourContact with water
And a means for contacting said NaBH_FourAnd water and
Hydrolyzing in the presence of the above catalyst by contacting
By causing the
Characterized by being configured to generate and store elementary gas
And a hydrogen cylinder (claim 3).

In the hydrogen cylinder of the present invention, NaBH ₄ and water are contained in advance in a pressure vessel, and when necessary, they are brought into contact with each other by the contact means to carry out a hydrolysis reaction to generate hydrogen gas. You can Besides, according to the present invention, it is possible to obtain the same effects as the above-mentioned invention, and it is possible to easily generate and store hydrogen gas in the pressure resistant container when necessary.

A third aspect of the invention is to generate and store hydrogen gas in the pressure resistant container by bringing NaBH ₄ and water into contact with each other in the presence of a catalyst to cause a hydrolysis reaction in the pressure resistant container. According to another aspect of the present invention, there is provided a method for storing hydrogen gas. According to the hydrogen gas storage method of the present invention, it is possible to obtain a hydrogen cylinder exhibiting the above-mentioned excellent effects, and it is possible to easily generate and store hydrogen gas in a pressure resistant container when necessary.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As NaBH ₄ in the hydrogen cylinders according to the first and second inventions, for example, powder or tablets in solid form can be used. As the water, for example, ion exchanged water, tap water,
In addition to seawater, rainwater, steam, etc., a material containing water can be used. Further, the catalyst may be applied to the pressure resistant container via a binder or the like, or the catalyst supported on a metal or an inorganic material may be mounted inside the pressure resistant container. In addition, NaBH ₄ and water can be charged from the material charging port at substantially the same time, or one of them can be charged first and then the other.

In the above-mentioned first invention (claim 1),
The hydrogen cylinder may be configured such that the NaBH ₄ is charged into the pressure resistant container in advance and incorporated therein, and the water is charged from the charging port when hydrogen gas is generated (claim 2). In this case, when it is necessary to generate hydrogen gas, only the water needs to be charged, and the separation and contact between the NaBH ₄ and water can be performed more easily.

Further, in the second aspect of the present invention (claim 3), the means for contacting NaBH ₄ and water is provided as described above. As the contact means, water can be put into a destructible container arranged inside the pressure vessel, and the container can be destroyed by the destructing means. Specifically, a capsule or balloon made of soft polymer or rubber or the like is placed in the pressure-resistant container, water is placed inside the pressure-resistant container, and the capsule or balloon is crushed by pressure or killed by a needle or the like. Water and NaBH ₄ can be contacted by destroying a balloon or the like.

In the first invention (Claim 1) and the second invention (Claim 3), the pressure resistant container may have a filling port for filling hydrogen gas (Claim 4). ). In this case, hydrogen gas can be generated by previously filling the pressure vessel with hydrogen gas from the filling port, using this hydrogen gas, and then contacting the NaBH ₄ with water. Therefore, it is possible to refill the same pressure vessel with hydrogen gas without supplying the hydrogen gas from the outside by using the hydrogen gas that was initially filled in the pressure vessel. Therefore, the amount of usable hydrogen gas per weight or volume of one hydrogen cylinder can be increased.

Further, it is preferable that the catalyst comprises a Co-based oxide (claim 5). In this case, the Co-based oxide can further promote the generation of the hydrogen gas. Examples of the Co-based oxide include LiCo
O ₂ , Co ₃ O ₄ or the like can be used.

The water is preferably used in a molar ratio of 2 to 5 times that of NaBH ₄ (claim 6). In this case, the above hydrolysis reaction can be performed almost without excess or deficiency, and after the reaction, NaB is placed in the pressure vessel.
The hydrogen gas can be generated more effectively without leaving much H ₄ or water. When the amount of water deviates from the amount of 2 to 5 times, it becomes difficult to carry out the hydrolysis reaction without excess or deficiency.

In the hydrogen gas storage method according to the third aspect of the present invention (claim 7), the NaBH ₄ is
For example, solid powder or tablets can be used. Further, as the water, for example, ion-exchanged water, tap water, seawater, rainwater, steam, and the like, or a material containing water can be used. Further, the catalyst may be applied to the pressure resistant container via a binder or the like, or the catalyst supported on a metal or an inorganic material may be mounted inside the pressure resistant container. In addition, NaBH from the above material input port
₄ and water can be added at about the same time,
It is also possible to throw either one first and then the other.

Further, it is preferable that the catalyst comprises a Co-based oxide (claim 8). In this case, the Co-based oxide can further promote the generation of the hydrogen gas. Examples of the Co-based oxide include LiCo
O ₂ , Co ₃ O ₄ or the like can be used.

The water is preferably used in a molar ratio of 2 to 5 times that of NaBH ₄ (claim 9). In this case, the above hydrolysis reaction can be performed almost without excess or deficiency, and after the reaction, NaB is placed in the pressure vessel.
The hydrogen gas can be generated more effectively without leaving much H ₄ or water.

[0021]

Embodiments of the present invention will be described below with reference to the drawings. (Embodiment 1) As shown in FIG. 1, a hydrogen cylinder 1 in this embodiment comprises a pressure vessel 2 provided with a gas discharge hole 21 and a material inlet 22, a catalyst 3 arranged in the pressure vessel 2, and a pressure vessel. 2 has a powder 4 made of NaBH ₄ previously charged therein. Then, when hydrogen gas is generated in the hydrogen cylinder 1, by introducing water 5 from the material charging port 22, NaBH ₄ in the pressure vessel 2 is changed.
The powder 4 and the water 5 are brought into contact with each other to cause a hydrolysis reaction in the presence of the catalyst 3. As described above, the hydrogen cylinder 1 is configured to generate and store hydrogen gas in the pressure vessel 2.

This will be described in detail below. In this example, the catalyst 3 is Pt—LiCo which is a Co-based oxide.
It consists of O ₂ . The amount of the water 5 used is 2 to 5 times the molar amount of the powder 4 of NaBH ₄ . Also,
Both the powder 4 of NaBH ₄ and the water 5 can be charged through the material charging port 22. In addition, the above Na
The powder 4 of BH ₄ can be replaced with a tablet.

As shown in FIG. 1, in this example, the pressure vessel 2 of the hydrogen cylinder 1 has a pressure resistance of 20 MPa or more. The pressure-resistant container 2 includes a body 20 that is a main body, and a lid 25 that sandwiches a sealing material 201 that is Teflon (registered trademark). In this example, the body 20 and the lid 25 are attached and detached by a screw structure with a pair of screw portions 202.

Further, the lid 25, the material inlet 2 for introducing the gas release hole 21, the powder 4 or water 5 such as of NaBH ₄ in a pressure vessel 2 which releases hydrogen gas to the outside of the pressure vessel 2
2. A valve 23 for opening the gas discharge hole 21 and a pressure measuring hole 24 for monitoring the pressure in the pressure vessel 2 are provided. Then, by loosening the valve 23, hydrogen gas can be released from the gas release hole 21, and a pressure gauge can be attached to the pressure measurement hole 24 to monitor the pressure in the pressure resistant container 2. .

As shown in FIG. 2, when the water 5 is injected from the material inlet 22, a syringe 26 is connected to the material inlet 22 and the injection needle 261 connected to the tip of the injector 26 is inserted into the pressure resistant container 2. Then, the syringe 26 can be operated to inject water 5 from the injection needle 261.

Further, as shown in FIG. 3, a sub-tank 61 is provided inside the pressure resistant container 2, and the catalyst 3 and NaBH _{4 are} added.
The powder 4 can be placed in the sub tank 61, and water 5 can be added to the sub tank 61 to cause the hydrolysis reaction. In this case, a gas hole 611 is provided in the upper portion of the sub-tank 61 so that the hydrogen gas generated by the hydrolysis reaction can be filled in the pressure resistant container 2. Also,
In this case, BaBO ₄ produced after the hydrolysis reaction can be deposited in the sub tank 61. Therefore, when the BaBO ₄ is collected and washed after the reaction, the sub-tank 61 can be removed from the pressure resistant container 2.

Further, as shown in FIG.
The lid 25 may not be provided with the material introduction port 22 and the catalyst 3 and the powder 4 of NaBH ₄ may be directly introduced into the body 20 by opening the lid 25 with respect to the body 20. Then, in this case, the lid 25 is closed again on the body 20 after the charging, and the water 5 is removed from the gas release hole 21.
Can be used.

In the hydrogen cylinder 1, the hydrolysis reaction is theoretically performed by the chemical reaction formula (NaBH ₄ + 2H).
₂ O → NaBO ₂ + 4H ₂ ). Then, if hydrogen gas is generated based on this chemical reaction formula, the hydrolysis reaction is theoretically in the vicinity of stoichiometry, that is, NaBH ₄ is 1 mol of H ₂ O.
It is possible to carry out 2 mol contact with each other efficiently without excess or deficiency. However, in this hydrolysis reaction, H
₂ O is decomposed to generate heat, part of H ₂ O evaporates and condenses on the wall surface of the pressure vessel 2. Therefore, the amount of H ₂ O is
It is preferable that NaBH ₄ is more than 2 mol per 1 mol and not more than 5 mol.

After the hydrolysis reaction is carried out, hydrogen gas H ₂ is produced and solid NaB is produced.
O ₂ is created in the pressure vessel 2. This NaBO ₂ becomes a residue after the above reaction is carried out, and is removed from the pressure vessel 2 after the hydrogen gas is generated. In addition, this N
Since aBO ₂ does not affect the hydrolysis reaction, it can be removed collectively after the hydrolysis reaction is performed in the pressure vessel 2 a plurality of times.

Further, as shown in FIG. 5, the amount of hydrogen gas that can be produced is defined as the hydrogen production efficiency, that is, NaBH ₄
Amount of produced hydrogen (wt%) relative to the amount of (H ₂ / NaBH
₄ ), by doubling the amount of water 5 with respect to the amount of powder 4 of NaBH ₄ , it is 18.5 to 20.3.
could be made to be wt%.

Next, the function and effect of this example will be described. As described above, the hydrogen cylinder 1 in this example is the pressure vessel 2
Hydrogen gas can be directly generated in the pressure resistant container 2 without being filled with hydrogen gas from the outside. That is,
In this example, hydrogen gas is produced by bringing the powder 4 of NaBH ₄ and water 5 into contact with each other in the pressure vessel 2 to cause a hydrolysis reaction. At this time, since the catalyst 3 is arranged in the pressure resistant container 2, the hydrolysis reaction is promoted by the pressure action of the hydrogen generation pressure, so that high-pressure hydrogen gas can be rapidly generated.

As described above, in the hydrogen cylinder 1, the pressure vessel 2 is supplied without supplying hydrogen gas from the outside.
High-pressure hydrogen gas can be generated inside, and the pressure-resistant container 2 can be filled with high-pressure hydrogen gas. Therefore, at a normal time when hydrogen gas is not required, it is possible to form a state in which there is no hydrogen gas in the pressure resistant container 2, and it is possible to eliminate the risk of storing hydrogen gas. Further, since hydrogen gas does not have to be supplied from the outside, a hydrogen gas supply source is not required.

[0033] In addition, as described above, the powder 4 of NaBH ₄
And water 5 are brought into contact with each other to generate hydrogen gas. for that reason,
Hydrogen gas can be easily generated by contacting the powder 4 of NaBH ₄ and water 5 only when necessary. Therefore, the hydrogen cylinder 1 can be used, for example, in an application requiring hydrogen gas in an emergency or in an emergency, or in a portable use.

(Embodiment 2) As shown in FIG. 6, in this embodiment,
This is an example of measuring the change in pressure in the pressure vessel 2 when the powder 4 of NaBH ₄ and water 5 are brought into contact with each other to carry out a hydrolysis reaction to generate hydrogen gas. Others are the same as those in the first embodiment. In this example, two kinds of reaction tests, that is, reaction tests 1 and 2 in which the amount of water 5 reacted with the powder 4 of NaBH ₄ are different were performed.

(Reaction Test 1) 2.5 g of Pt-LiCoO ₂ as a catalyst 3 was placed in a pressure vessel 2 having a volume of 237 cc.
5g of powder 4 of NaBH ₄ is built in, and this NaBH 4
_The hydrolysis reaction was carried out by introducing into the pressure resistant container 2 water 5 in an amount 3.15 times the molar ratio of the powder 4 of 4. At this time, the hydrolysis reaction became active after about 2 minutes, and the pressure temporarily increased to about 12 MPa and then became about 5 MPa. In this example, all references to pressure refer to gauge pressure. The same applies hereinafter.

(Reaction Test 2) 2.5 g of Pt-LiCoO ₂ as a catalyst 3 was placed in a pressure vessel 2 having a volume of 237 cc.
5g of powder 4 of NaBH ₄ is built in, and this NaBH 4
Was charged water 5 2.10 times the amount in mole ratio to ₄ powder 4, hydrolysis reaction was performed. At this time, the NaB
Shortly after the contact between the H ₄ powder 4 and the water 5, the hydrolysis reaction was activated, and the pressure temporarily increased to about 10 MPa, and then became about 5 MPa.

The above results are summarized as follows. That is, the amount of hydrogen gas produced mainly depends on the amount of the powder 4 of NaBH ₄ , and the amount of water 5 that reacts with it is twice or more in terms of molar ratio, so that the amount of hydrogen gas is close to the total amount.
The powder 4 of aBH ₄ can be reacted. On the other hand,
When the amount of water 5 is 5 times or more in terms of molar ratio, the amount of hydrogen gas produced does not change so much, but a large amount of unreacted water 5 may remain in the pressure vessel 2 after the reaction. Further, if the amount of water 5 is less than twice the molar ratio, the reaction of the powder 4 of NaBH ₄ is restricted, and the unreacted NaB 4 after the reaction is restricted.
The powder 4 of H ₄ remains.

Although there is a delay in the hydrolysis reaction before the reaction starts, the powder 4 of NaBH ₄ close to the total amount can be reacted instantaneously after the reaction starts. Since the pressure-resistant container 2 is sealed, the hydrogen gas generated by the hydrolysis reaction is
Increase the pressure inside. Therefore, it is possible to easily fill the hydrogen cylinder 1 with high-pressure hydrogen gas simply by performing the above reaction.

Further, as shown in FIG. 7, when the amount of the water 5 (molar ratio H ₂ O / NaBH ₄ ) is increased, Na increases.
It was found that the reaction delay time from contacting the powder 4 of BH ₄ with water 5 until the reaction occurs becomes long. That is, the relationship between the amount of water 5 and the reaction delay time is considered to be proportional. This means that in the pressure vessel 2,
It shows that the reaction does not occur immediately after contacting the powder 4 of NaBH ₄ and water 5.

The nature of this reaction delay time should be applied to applications where there is a time lag between when the powder 4 of NaBH ₄ or water 5 is charged into the pressure vessel 2 and when the above reaction occurs. You can That is, if the amount of water 5 is increased, the time until the reaction occurs after the powder 4 of NaBH ₄ and water 5 are brought into contact with each other can be delayed. for that reason,
For example, from the material inlet 22 of the pressure resistant container 2 to NaBH
_{Even if} the powder 4 or the water 5 of 4 is put into contact with each other, a reaction does not occur during the feeding. Therefore, it is possible to prevent the hydrogen gas from flowing back from the material charging port 22 to the outside of the pressure vessel 2 due to the reaction occurring during this process.

Thus, the water 5 is the same as the NaBH ₄
The hydrogen gas can be efficiently generated by using a molar ratio of 2 to 5 times that of the powder 4, and the excellent hydrogen cylinder 1 can be produced by utilizing the property of the reaction delay time. Obtainable.

(Embodiment 3) In this embodiment, FIG. 8, FIG. 9 and FIG.
As shown in, not pressure-resistant container 2 having a material inlet 22, allowed to built in a separated state so as not to contact with each other powder 4 and water 5 above NaBH ₄ to the pressure-resistant container 2, This is an example of contacting the powder 4 of NaBH ₄ with water 5 by the contact means 4.

The contact means 4 is, as shown in FIG.
It is configured to have a sub tank 61 provided inside the pressure resistant container 2, a balloon 62 provided inside the sub tank 61, and a breaking needle 63 with a lever 631 capable of breaking the balloon 62. The catalyst 3 and the powder 4 of NaBH ₄ are placed in the sub tank 61, and the water 5 is placed in the balloon 62. Then, to break the balloon 62 by destroying the needle 63 by operating the lever 631, by contacting the powder 4 and water 5 catalyst 3 and NaBH _4, perform the hydrolysis reaction. Others are the same as those in the first embodiment.

The hydrogen cylinder 1 in this embodiment incorporates a powder 4 and water 5 of NaBH ₄ in advance pressure-resistant container 2,
When necessary, they can be brought into contact with each other by the contact means 6 to cause a hydrolysis reaction to generate hydrogen gas. Therefore, what is needed to produce hydrogen gas (catalyst 3, the powder 4 and water 5 of NaBH ₄₎ all can keep in pressure-resistant container 2, without supplying to the pressure vessel 2 after Good. Therefore, according to this example, hydrogen gas can be more easily generated and stored in the pressure resistant container 2 when necessary. In addition, it is possible to obtain the same effect as that of the first embodiment.

(Embodiment 4) In this embodiment, the pressure vessel 2 is
This is an example having a filling port 23 for filling hydrogen gas. Then, in this example, previously filled with hydrogen gas in advance from the filling port 23 to the pressure vessel 2, after using the hydrogen gas, the powder 4 above NaBH ₄ and water 5 and a pressure vessel 2 To produce a hydrogen gas. The filling port 23 can also be used as the material charging port 22, and hydrogen gas can be charged from the material charging port 22. In this case, when filling the hydrogen gas from the material charging port 22, the valve 23 is opened and the gas discharge hole 21 is closed. Others are the same as those in the first embodiment.

In this example, the invention products 1 to 4 having different amounts of the powder 4 of NaBH ₄ , the water 5 and the catalyst 3 and the comparison products 1 and 2 for comparison with them were tested. . Further, in this example, the hydrogen gas is used as a hydrogen source of the fuel cell.

(Invention product 1) The pressure vessel 2 has an internal volume of 23
A high pressure vessel TVS-1 manufactured by Beadrex having a capacity of 1 cc, an outer volume of 480 cc and a weight of 2.3 kg was used. Into this pressure vessel 2, 5 g of powder 4 of NaBH ₄ and Pt-LiCo were added.
Add 2.5 g of O ₂ until the pressure reaches about 10 MPa,
That is, about 1.69 g of hydrogen gas was filled. This hydrogen gas was used as the hydrogen source of the fuel cell until the pressure inside the pressure vessel 2 became about 0 MPa. After that, 5 g of water produced by the fuel cell was added as water 5 and sealed. Then, about 20 seconds after the water 5 was added, the pressure in the pressure vessel 2 increased to about 5 MPa, and about 0.85 g of hydrogen was produced.

(Invention product 2) The pressure vessel 2 has an internal volume of 23
A high pressure vessel TVS-1 manufactured by Beadrex having a capacity of 1 cc, an outer volume of 480 cc and a weight of 2.3 kg was used. In this pressure vessel 2, 10 g of powder 4 of NaBH ₄ and Pt-LiC were added.
5 g of oO ₂ was charged, and hydrogen gas was charged until the pressure reached about 10 MPa as a gauge pressure, that is, about 1.64 g of hydrogen gas. The hydrogen gas is used as the hydrogen source of the fuel cell and the pressure vessel 2
It was used until the internal pressure became about 0 MPa. After that, 10 g of water produced by the fuel cell was added as water 5 and sealed. About 18 seconds after putting this water 5, the pressure vessel 2
The internal pressure rises to approximately 10.2 MPa, approximately 1.84 g
Generated hydrogen.

(Invention product 3) The pressure-resistant container 2 has an internal volume of 11
A high pressure vessel TVS-N2 made by Beadlex, having 7 cc, an outer volume of 240 cc and a weight of 2.2 kg was used. Into this pressure vessel 2, 5 g of powder 4 of NaBH ₄ and Pt-LiC were added.
2.5 g of oO ₂ was added, and the pressure was about 20 MPa in gauge pressure.
Until about 1.55 g hydrogen gas was charged.
This hydrogen gas was used as the hydrogen source of the fuel cell until the pressure inside the pressure vessel 2 became about 0 MPa. After that, 5 g of water produced by the fuel cell was added as water 5 and sealed.
And, about 22 seconds after putting this water 5, the pressure inside the pressure vessel 2 rises to about 10 MPa, and about 0.87 g
Generated hydrogen.

(Invention product 4) The pressure vessel 2 has an internal volume of 11
A high pressure vessel TVS-N2 made by Beadlex, having 7 cc, an outer volume of 240 cc and a weight of 2.2 kg was used. In this pressure vessel 2, 10 g of powder 4 of NaBH ₄ and Pt-Li were added.
5 g of CoO ₂ was charged, and hydrogen gas of about 1.47 g was charged until the pressure became about 20 MPa in gauge pressure. This hydrogen gas was used as the hydrogen source of the fuel cell until the pressure inside the pressure vessel 2 became about 0 MPa. afterwards,
As water 5, 10 g of fuel cell produced water was added and sealed. Then, about 24 seconds after the water 5 was added, the pressure in the pressure vessel 2 increased to about 20 MPa, and about 1.85 g of hydrogen was produced.

(Comparative product 1) The pressure vessel 2 has an internal volume of 23
A high pressure vessel TVS-1 manufactured by Beadrex having a capacity of 1 cc, an outer volume of 480 cc and a weight of 2.3 kg was used. In the pressure vessel 2, until the pressure reaches about 10 MPa in gauge pressure,
That is, about 1.73 g of hydrogen gas was charged. This hydrogen gas was used as the hydrogen source of the fuel cell until the pressure inside the pressure vessel 2 became about 0 MPa.

(Comparative product 2) The pressure vessel 2 has an internal volume of 11
A high pressure vessel TVS-N2 made by Beadlex, having 7 cc, an outer volume of 240 cc and a weight of 2.2 kg was used. The pressure vessel 2 was filled with hydrogen gas until the pressure reached about 20 MPa in gauge pressure, that is, about 1.63 g of hydrogen gas. And
This hydrogen gas was used as the hydrogen source of the fuel cell until the pressure inside the pressure vessel 2 became about 0 MPa.

Table 1 shows the results of the above-mentioned operations as the hydrogen gas storage capacity. That is,
In the table, hydrogen storage capacity (g) is the same as the pressure resistant container 2
Indicates the amount of hydrogen (g) that can be stored inside, and the weight storage density (g / kg) is the amount of hydrogen that can be stored with respect to the weight (kg) of the pressure vessel 2. The amount (g) is shown. The volume storage density (g / L) indicates the amount (g) of hydrogen that can be stored with respect to the outer volume (L) of the pressure resistant container 2.

[0054]

[Table 1]

As can be seen from the table, the invention products 1 to 4 are:
After using the initially filled hydrogen gas, hydrogen gas can be generated in the pressure resistant container 2 and replenished to the pressure resistant container 2. Therefore, the value of the storage capacity of any hydrogen gas is about twice as large as that of the comparative products 1 and 2. Therefore, as described above, it is found that the hydrogen gas storage capacity is significantly increased by generating the hydrogen gas in the pressure resistant container 2. When the hydrogen cylinder 1 is used as a hydrogen source for a fuel cell, it can increase the amount of hydrogen gas that can be supplied to the hydrogen cell and can be used comfortably as a hydrogen source for a fuel cell. be able to.

Since the hydrogen cylinder 1 has a high hydrogen gas storage capacity as described above, the amount of hydrogen covered by about two hydrogen cylinders in the conventional hydrogen gas storage method is one hydrogen cylinder. You can cover one. Therefore,
According to the hydrogen cylinders 1 of the invention products 1 to 4, a large amount of hydrogen gas can be used by using the same pressure resistant container 2 without replenishing hydrogen gas from the outside.

Further, since the above hydrolysis reaction is carried out in the sealed pressure-resistant container 2, by changing the relationship between the amount of NaBH ₄ and the internal volume of the pressure-resistant container 2, the hydrogen gas after the hydrogen gas is generated is generated. The pressure of the cylinder 1 can be easily changed. For example, the pressure of the hydrogen cylinder 1 can be increased by increasing the amount of NaBH ₄ with respect to the internal volume of the pressure container 2, and the pressure of the pressure container 2 with respect to the amount of NaBH ₄ can be increased.
It can also be increased by reducing the internal volume of the.

[0058] Further, the hydrogen cylinder 1 is normal is used to fill the hydrogen gas, when the hydrogen gas is about to disappear in the absence is a source of hydrogen gas, the powder 4 and water 5 above NaBH ₄ Is hydrolyzed to produce hydrogen gas,
It is possible to avoid such an emergency. As such an application, for example, it is considered that the hydrogen cylinder 1 is mounted and used in a hydrogen gas specification vehicle or the like that runs on hydrogen as fuel. In addition, when hydrogen gas is normally used by being filled from the outside, it is used in an emergency, that is, when the hydrogen gas in the hydrogen cylinder 1 runs low (unlikely to run out of gas).
In addition, the above hydrolysis reaction can be performed to refill the hydrogen cylinder 1 with hydrogen gas to cope with this emergency.

[Brief description of drawings]

FIG. 1 is a cross-sectional explanatory view showing a hydrogen cylinder according to a first embodiment.

FIG. 2 is a view showing a hydrogen cylinder according to the first embodiment, and a cross-sectional explanatory view showing a state in which a syringe is connected to the material inlet.

FIG. 3 is a cross-sectional explanatory view showing a hydrogen cylinder when a sub-tank is arranged inside the pressure resistant container in the first embodiment.

FIG. 4 is a cross-sectional explanatory view showing a hydrogen cylinder in Example 1 when a material inlet is not provided.

FIG. 5 shows the molar ratio (H ₂ O / NaBH) in Example 1.
₄ ) A graph showing the relationship between the hydrogen production amount (wt%).

FIG. 6 is a graph showing the relationship between time (min) and pressure (MPa) in the pressure resistant container when NaBH ₄ and water are hydrolyzed in Example 2.

FIG. 7 shows the molar ratio (H ₂ O / NaBH) in Example 2.
₄ ) A graph showing the relationship between (mol / mol) and the reaction delay time (s).

FIG. 8 is a top view showing a hydrogen cylinder according to a third embodiment.

FIG. 9 is a diagram showing a hydrogen cylinder according to a third embodiment and is a cross-sectional view taken along the line AA of FIG.

FIG. 10 is a diagram showing a hydrogen cylinder in Example 3,
9 is a cross-sectional view taken along the line BB of FIG.

[Explanation of symbols]

1. ． ． Hydrogen cylinder, 2. ． ． Pressure resistant container, 21. ． ． Gas discharge hole, 22. ． ． Material input port, 3. ． ． Catalyst, 4. ． ． NaBH ₄ powder 5. ． ． Water, 6. ． ． Contact means,

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 3E072 AA01 DB03 EA10                 4G069 AA03 BB06B BC04B BC67B                       BC75B CB81 DA05 DA06

Claims (9)

[Claims] A pressure vessel 1. A provided with gas discharge holes and the material inlet, and a catalyst disposed in the pressure vessel was charged with NaBH ₄ and water from the material inlet, the NaBH ₄
A hydrogen cylinder, which is configured to generate and store hydrogen gas in the pressure-resistant container by causing a hydrolysis reaction in the presence of the catalyst by bringing water and water into contact with each other. 2. The hydrogen cylinder according to claim 1, wherein:
A hydrogen cylinder, characterized in that the NaBH ₄ is charged into the pressure resistant container in advance and incorporated therein, and the water is charged from the charging port when hydrogen gas is generated. 3. A pressure-resistant container provided with a gas release hole, a catalyst arranged in the pressure-resistant container, NaBH ₄ and water contained in the pressure-resistant container in a separated state so as not to come into contact with each other, and the NaBH ₄ And contacting means for contacting water, the contacting means for contacting the NaBH ₄ with water to cause a hydrolysis reaction in the presence of the catalyst, thereby producing hydrogen gas in the pressure vessel. A hydrogen cylinder configured to generate and store hydrogen. 4. The method according to claim 1, wherein
A hydrogen cylinder, wherein the pressure vessel has a filling port for filling hydrogen gas. 5. The method according to any one of claims 1 to 4,
A hydrogen cylinder characterized in that the catalyst is made of a Co-based oxide. 6. The method according to any one of claims 1 to 5,
The hydrogen cylinder is characterized in that the water is used in a molar ratio of 2 to 5 times that of NaBH ₄ . 7. A pressure-resistant container containing Na in the presence of a catalyst.
A method for storing hydrogen gas, wherein BH ₄ and water are brought into contact with each other to cause a hydrolysis reaction to generate and store hydrogen gas in the pressure resistant container. 8. The method for storing hydrogen gas according to claim 7, wherein the catalyst comprises a Co-based oxide. 9. The method for storing hydrogen gas according to claim 7, wherein the water is used in a molar ratio of 2 to 5 times that of NaBH ₄ .